Method of crystallizing a nitride III-V compound semiconductor layer on a sapphire substrate

ABSTRACT

To improve crystallographic property of a nitride III-V compound semiconductor layer grown on a sapphire substrate, a plurality of recesses are made on a major surface of the sapphire substrate, and the nitride III-V compound semiconductor layer is grown thereon. At least a part of the inner surface of each recess makes an angle not less than 10 degrees with respect to the major surface of the sapphire substrate. The recesses are buried with nitride III-V compound semiconductor crystal having a higher Al composition ratio than the nitride III-V compound semiconductor layer, such as Al x Ga 1-x N crystal whose Al composition ratio x is 0.2 or more, for example. Each recess has a depth not less than 25 nm and a width not less than 30 nm. The recesses may be made either upon thermal cleaning of the sapphire substrate or by using lithography and etching, thermal etching, or the like.

The present application is a continuation of U.S. patent applicationSer. No. 09/795,844 filed Feb. 28, 2001, now U.S. Pat. No. 7,033,854,which is a divisional of U.S. application Ser. No. 09/334,666 filed Jun.17, 1999, now U.S. Pat. No. 6,232,623, which claims priority to JapaneseApplication No. P10-180930 filed Jun. 26, 1998, all of which areincorporated herein by reference to the extent permitted by law.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a semiconductor device and its manufacturingmethod especially suitable for application to semiconductor lasers andlight emitting diodes or electron mobility devices using nitride III-Vcompound semiconductors such as GaN.

2. Description of the Related Art

Heretofore, semiconductor lasers and light emitting diodes have beendeveloped, using nitride III-V compound semiconductors made of group IIIelements such as Al, Ga and In and group V elements including N, asrepresented by GaN, as their light emitting materials in the rangeextending from green or blue to ultraviolet. On the other hand, althoughcontinuous oscillation at room temperatures has been realized withsemiconductor lasers, there is still the need for further improvement incrystallographic property of nitride III-V compound semiconductorstoward their longer lifetime. For this purpose, a technique forimproving crystallographic property of GaN such as ELOG-GaN (EpitaxiallyLaterally Overgrown GaN) is being used and actually performing effects.However, it is also desired to further improve the basis of thetechnique, namely, crystallographic property of nitride III-V compoundsemiconductors grown on crystalline substrates.

Usually used as a substrate crystal is sapphire or SiC. Nitride III-Vcompound semiconductor layers are grown on such a crystalline substrateafter it is processed in a growth apparatus for sufficiently smoothing,polishing and cleaning its surface. In order to manufacture a desiredsemiconductor device, it is necessary to make various multi-layeredstructures having surfaces or interface structures which are flat in theatomic level. Therefore, also for substrates, surface cleaning methodsand growth methods capable of maintaining or making their surfaces flatare being used.

There has also been proposed a method which improves crystallineproperty of nitride III-V compound semiconductor layers by slightlyinclining a crystalline substrate surface such that layers be grownthereon in a step flow mode (Japanese Patent Laid-Open Publication No.hei 7-201745).

When using a GaAs substrate or InP substrate, a technique is being used,which first grows a buffer layer on a substrate having formed on its(001) surface a (111) B-oriented diffraction grating for the purpose ofreflecting guided light in the waveguide. (Japanese Patent Laid-OpenPublication No. hei 8-264901).

Also known are a method for improving crystalline property byinterposing an AlN buffer layer (Japanese Patent Laid-Open PublicationNo. hei 2-229476) or a GaN or AlGaN buffer layer (Japanese Patent LaidOpen Publication No. hei 4-297023) between a sapphire substrate and anitride III-V compound semiconductor thereon; a method for improving bynitrifying a sapphire substrate surface (Japanese Patent Laid OpenPublication No. hei 5-41541). Also known is a method which sequentialstacks a plurality of buffer layers different in lattice constant toreduce differences in lattice constant between the substrate and thebuffer layer and between the buffer layer and an epitaxial layer thereon(Japanese Patent Laid Open Publication No. hei 9-63962).

It is generally noted that “fluctuation” in crystalline orientationexists in nitride III-V compound semiconductor crystals grown on asapphire or SiC substrate. That is, these nitride III-V compoundsemiconductor crystals are “mosaic crystals”. Fluctuation in crystallineorientation is roughly classified into two components, namely, “twist”mosaic components which fluctuate in a rotational direction around anaxis vertical to the substrate surface, and “tilt” mosaic componentswhich are fluctuation in axial orientation from a vertical direction.Magnitude of these fluctuations is noted to be normally 0.01 to 0.5°.Causes of fluctuation in crystalline orientation are considered to liein a difference in crystalline structure between the substrate and anitride III-V compound semiconductor layer grown thereon and a largedifference in lattice constant between them. It is also considered to beanother factor that, crystal orientation is not accurately carried overduring growth from the sapphire substrate because of relatively weakatomic coupling between stable sapphire crystal and a nitride III-Vcompound semiconductor crystal as compared with those inside thesecrystals.

Due to such mosaic crystalline property, in semiconductor light emittingdevices using nitride III-V compound semiconductors, improvement indevice characteristics has been prevented, by degradation in emissionefficiency, and there are problems such as short lifetime regardingreliability required for the device.

SUMMARY OF THE INVENTION

It is therefore an object of the invention to provide a semiconductordevice and its manufacturing method capable of improving crystallineproperty of a nitride III-V compound semiconductor layer grown on asapphire substrate.

The present invention discloses optimum surface states of a sapphiresubstrate for improving crystalline property of nitride III-V compoundsemiconductors grown on the sapphire substrate. It has been believedthat being smoother is more desirable for surfaces of sapphiresubstrates, and efforts have been made for smoothing. For example,Japanese Patent Laid-Open Publication No. hei 8-83802, for example,proposes a technique for obtaining a super-smooth substrate surfaceexclusively made of terrace surfaces substantially equal in crystallineorientation and having a straight, regular step site, by selecting aheating time and a heating temperature in accordance with the surfaceorientation upon annealing a sapphire substrate by raising thetemperature to 900° C. or higher in a normal pressure atmosphere.

However, the present invention discloses that it is better to positivelymake recesses on the surface of a sapphire substrate, in contrast tosmoothing mentioned above, for the purpose of increasing crystallineproperty of nitride III-V compound semiconductors grown on the sapphiresubstrate. This is for the reason explained below.

In the process of crystal growth (including vapor-phase growth andsolid-phase growth) on a smooth sapphire substrate surface, crystallineorientation of a nitride III-V compound semiconductor crystal undergrowth is determined exclusively by interaction between atoms of thenitride III-V compound semiconductor and atoms of the sapphire crystalinterposing only one interface parallel to the substrate surface.Therefore, if the interaction at the interface is not large, fluctuationin crystalline orientation mentioned above increases. Especially,control of fluctuation in crystalline orientation along the plane (twistcomponent) becomes weak. In contrast, along the interface havingrecesses, crystalline orientation can be controlled as a result oflimitation of crystalline orientation by lateral constraint forceapplied through a slanted crystal surface not parallel to the substrate.Therefore, it is possible to establish more precise coincidence incrystalline orientation between the sapphire substrate and a nitrideIII-V compound semiconductor crystal grown thereon.

In a method using a step-shaped slightly angled substrate uniform incrystalline orientation, constraint of crystalline orientation is onedirection. In contrast, in the case where a sapphire substrate surfacehas formed recesses, growth of a nitride III-V compound semiconductor onthe sapphire substrate is restricted by a plurality of crystaldirections and crystal surfaces. Therefore, a larger effect can beobtained regarding coincidence in crystalline orientation between thesapphire substrate and a nitride III-V compound semiconductor layergrown thereon.

The present invention has been made on the above-explained researches.

According to the first aspect of the invention, there is provided asemiconductor device using a nitride III-V compound semiconductor layergrown on a sapphire substrate, comprising:

recesses made on the sapphire substrate along an interface thereof withthe nitride III-V compound semiconductor layer.

According to the second aspect of the invention, there is provided amanufacturing method of a semiconductor device using a nitride III-Vcompound semiconductor layer grown on a sapphire substrate, comprising:

first forming recesses on a major surface of the sapphire substrate, andthereafter growing the nitride III-V compound semiconductor layer on themajor surface of the sapphire substrate.

In the present invention, from the viewpoint of restricting growth by aplurality of crystalline directions and crystal surfaces when growingthe nitride III-V compound semiconductor layer on the sapphire substrateto ensure more precise coincidence in crystalline orientation betweenthe sapphire substrate and the nitride III-V compound semiconductorlayer grown thereon, at least a part of the inner surface of each recesson the sapphire substrate is preferably angled by 10 degrees or morefrom one major surface of the sapphire substrate. As to the size of eachrecess, its depth is preferably not smaller than 25 nm and the width isnot smaller than 30 nm, from the same viewpoint. Alternatively, from theviewpoint of facilitating diffusion of Al from the sapphire substrate asexplained later, depth of each recess is 10 nm or more, and its width is30 nm or more. Width of each recess is preferably 5 μm or less, andtypically 2 μm or less.

In the present invention, one major surface of the sapphire substrate istypically made up of surfaces inclined by a slight angle from the (0001)plane (so-called c plane) or the (0001) plane of the sapphire crystal.The slight angle herein means any angle within 10 degrees. In the casewhere one major surface of the sapphire substrate includes thesesurfaces, various crystalline planes may appear on inner surfaces of therecesses. More specifically, the {11–26} plane and the {11–29} plane ofsapphire crystal, for example, appear. According to measurement ofangles of crystalline planes on inner surfaces of recesses actuallymade, these two crystalline planes or planes with an angle between themwere confirmed, although depending upon recesses.

In this invention, the recesses of the sapphire substrate after growthof the nitride III-V compound semiconductor layer are plugged withnitride III-V compound semiconductor crystal having a uniformcrystalline orientation. However, all of the recesses need not be alwaysplugged with nitride III-V compound semiconductor crystal. The nitrideIII-V compound semiconductor plugged into the recesses and having auniform crystalline orientation can be made by first growing a bufferlayer of a nitride III-V compound semiconductor on the sapphiresubstrate having formed the recesses on its major surface and thereafterannealing it at a higher temperature. This method is suitable when usinga process of first growing a buffer layer of a nitride III-V compoundsemiconductor on a sapphire substrate at a lower temperature andthereafter growing the nitride III-V compound semiconductor layer on thebuffer layer at a higher substrate temperature. However, if the processfrom growth of the buffer layer to growth of the nitride III-V compoundsemiconductor layer thereon is progressed while continuously increasingthe substrate temperature from a low temperature to a high temperature,then a multi-layered structure with no irregular interface caused byinterruption of growth can be realized. As an alternative method, it ispossible to grow the nitride III-V compound semiconductor layer directlyon the sapphire substrate without growing the buffer layer whileincreasing the substrate temperature from a low temperature to a hightemperature so as to plug the nitride III-V compound semiconductorcrystal into the recesses of the sapphire substrate. More specifically,growth of the nitride III-V compound semiconductor layer is started froma substrate temperature around 500 to 520° C., for example, and thegrowth is continued while increasing the substrate temperature to 1000through 1100° C. Then, when the substrate temperature rises to 1000through 1100° C., the growth is still continued maintaining thesubstrate temperature. However, if a layer containing In, such as GaInNlayer is to be grown as the nitride III-V compound semiconductor, it isgrown at a substrate temperature within 700 to 800° C.

It can be known from the presence of absence of moire fringes through atransmission electron microscope that nitride III-V compoundsemiconductor crystal having a uniform crystalline orientation is formedin the recesses on the sapphire substrate. For example, on atransmission electron microscopic image taken by exciting at least(0002) reflection of nitride III-V compound semiconductor crystal and(0006) reflection of sapphire crystal, by observing moire fringes bythese lattice surfaces, which appear inside the recesses on the sapphiresubstrate, growth of nitride III-V compound semiconductor crystal havinga uniform crystalline orientation can be confirmed. These moire fringeshave a distance depending on components and composition of nitride III-Vcompound semiconductor crystal which has been grown.

In this invention, typically made to bury recesses on the sapphiresubstrate is a buffer layer made of nitride III-V compound semiconductorcrystal incorporating Al diffusing from the sapphire substrate made ofAl₂O₃ and having a higher Al composition ratio along the interfacebetween the sapphire substrate and the nitride III-V compoundsemiconductor layer thereon. The nitride III-V compound semiconductorcrystal with a higher Al composition ratio may be buried only in therecesses on the sapphire substrate. Since the recesses are provided onthe sapphire substrate along the interface with the buffer layer, thecontact area between the sapphire substrate and the buffer layerincreases only by the areas of the inner surface of the recesses.Therefore, Al diffuses easily from the sapphire substrate to the bufferlayer. For example, in the case where the nitride III-V compoundsemiconductor layer is made of Al_(x1)Ga_(1−x1−y1)In_(y1)N (0 x1 1, 0 y11, 0 x1+y1 1) and the nitride III-V compound semiconductor crystal ismade of Al_(x2)Ga_(1−x2−y2)In_(y2)N (0 x2 1, 0 y2 1, 0 x2+y2 1), x2−x10.1 is preferably satisfied. As a result of the nitride III-V compoundsemiconductor crystal with a higher Al composition ratio being made, thefollowing effects are obtained. That is, if the nitride III-V compoundsemiconductor layer is a GaN layer, for example, the nitride III-Vcompound semiconductor crystal with a higher Al composition ratio shouldbe AlGaN crystal. This AlGaN crystal continuously couples the sapphiresubstrate and the GaN layer via Al, and alleviates the difference inlattice constant between the sapphire substrate and the GaN layerbecause AlGaN crystal has a lattice constant nearer to the sapphiresubstrate than the GaN layer. Additionally, dislocation of mismatchingcaused by a difference in lattice constant can be decreased. The nitrideIII-V compound semiconductor crystal with a higher Al composition ratiocan be made by annealing during the substrate temperature beingincreased after growth of the buffer layer at a low temperature.Alternatively, if the nitride III-V compound semiconductor layer isdirectly growing on the sapphire substrate, without growing the bufferlayer, while increasing the substrate temperature from a low temperatureto a high temperature, the nitride III-V compound semiconductor crystalcan be made in the process of increasing the substrate temperature.Furthermore, from the viewpoint of effectively diffusing Al from thesapphire substrate, a layer containing Al and N is preferably made bynitrifying the major surface of the sapphire substrate by exposing it toa gas containing nitrogen prior to the growth. In these cases, since therecesses are formed on the sapphire substrate, the contact area alongthe interface between the sapphire substrate and the layer grown thereonincreases, and diffusion and reaction of Al are promoted.

It can be confirmed by observing moire fringes through transmissionelectron microscopy that the nitride III-V compound semiconductorcrystal with a higher Al composition ratio is formed along the interfacebetween the sapphire substrate and the nitride III-V compoundsemiconductor layer. More specifically, it is confirmed by observingmoire fringes with a distance of 0.8 to 1.7 nm along the interfaceregion on a transmission electron microscopic image taken by exciting atleast (0002) reflection of the nitride III-V compound semiconductorcrystal and (0006) reflection of sapphire substrate, or by observingmoire fringes with a distance of 1 to 2.1 nm along the interface regionon a transmission electron microscopic image taken by exciting at least(01–10) reflection of the nitride III-V compound semiconductor crystaland (11–20) reflection of sapphire substrate, or by observing moirefringes with a distance of 0.6 to 1.2 nm on a transmission electronmicroscopic image taken by exciting at least (0–220) reflection of thenitride III-V compound semiconductor crystal and (03–30) reflection ofsapphire crystal.

In the present invention, the nitride III-V compound semiconductor ismade up of at least one group III element selected from the groupconsisting of Ga, Al, In and B and one or more group V elements whichincludes N and may additionally include As or P. Specific examplesthereof are GaN, InN, AlN, AlGaN, GaInN and AlGaInN.

In this invention, metal organic chemical vapor deposition (MOCVD) ormolecular beam epitaxy (MBE), for example may be used for growth of thenitride III-V compound semiconductor layer.

In this embodiment, the semiconductor device may be any typeessentially. Specific examples thereof are light emitting devices suchas semiconductor laser or light emitting diode, and electron mobilitydevices such as GaN FET.

According to the invention having the above-summarized features, sincethe recesses are made on one major surface of the sapphire substrate,growth of the nitride III-V compound semiconductor layer on the sapphiresubstrate can be controlled by a plurality of crystalline directions andcrystalline planes. As a result, precise coincidence in crystallineorientation is ensured between the sapphire substrate and the nitrideIII-V compound semiconductor grown thereon.

The above, and other, objects, features and advantage of the presentinvention will become readily apparent from the following detaileddescription thereof which is to be read in connection with theaccompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross-sectional view taken along a plane vertical to thecavity lengthwise direction of a GaN semiconductor laser according tothe first embodiment of the invention;

FIG. 2 is a cross-sectional view showing a part of the GaN semiconductorlaser according to the first embodiment of the invention in an enlargedscale;

FIGS. 3A to 3F are plan views showing plan-view configurations ofrecesses to be formed on a surface of a c-plane sapphire substrate inthe GaN semiconductor laser according to the first embodiment of theinvention;

FIG. 4 is a cross-sectional view for explaining a manufacturing methodof the GaN semiconductor laser according to the first embodiment of theinvention;

FIG. 5 is a cross-sectional view for explaining a manufacturing methodof the GaN semiconductor laser according to the first embodiment of theinvention;

FIG. 6 is a schematic diagram showing a sequence of substratetemperatures in the manufacturing method of the GaN semiconductor laseraccording to the first embodiment of the invention;

FIG. 7 is a cross-sectional view for explaining a manufacturing methodof a GaN semiconductor laser according the third embodiment of theinvention;

FIG. 8 is a schematic diagram showing a sequence of substratetemperatures in the manufacturing method of the GaN semiconductor laseraccording to the fourth embodiment of the invention;

FIG. 9 is a cross-sectional view showing a part of a GaN semiconductorlaser according to the fifth embodiment of the invention in an enlargedscale;

FIG. 10 is a cross-sectional view for explaining a manufacturing methodof the GaN semiconductor laser according the fifth embodiment of theinvention;

FIG. 11 is a cross-sectional view showing a part of a GaN semiconductorlaser according to the sixth embodiment of the invention in an enlargedscale; and

FIG. 12 is a cross-sectional view for explaining a manufacturing methodof the GaN semiconductor laser according the sixth embodiment of theinvention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Explained below are embodiments of the invention with reference to thedrawings. In all drawings illustrating the embodiments, the same orequivalent parts or components are labeled with common referencenumerals.

FIG. 1 shows a GaN semiconductor laser according to the first embodimentof the invention, and FIG. 2 shows a part of the GaN semiconductor lasernear the substrate surface in an enlarged scale. The GaN semiconductorlaser has a SCH structure (separate confinement hetero-structure).

As shown in FIGS. 1 and 2, in the GaN semiconductor laser according tothe first embodiment, sequentially stacked on a c-plane sapphiresubstrate 1 via a GaN buffer layer 2 are: an undoped GaN layer 3, n-typeGaN contact layer 4, n-type AlGaN cladding layer 5, n-type GaN opticalguide layer 6, active layer 7 with a Ga_(1−x)In_(x)N/Ga_(1−y)In_(y)Nmulti quantum well structure, p-type AlGaN cap layer 8, p-type GaNoptical guide layer 9, p-type AlGaN cladding layer 10 and p-type GaNcontact layer 11. The p-type AlGaN cap layer 8 prevents decomposition ofInN from the active layer 7 of the Ga_(1−x)In_(x)In_(x)N/Ga_(1−y)In_(y)Nmulti quantum well structure and prevents overflow of electrons from theactive layer 7 during growth of the p-type GaN optical guide layer 9,p-type AlGaN cladding layer 10 and p-type GaN contact layer 11 at atemperature around 1000° C.

The GaN buffer layer 2 is 30 nm thick, for example, and the undoped GaNlayer 3 is 1 μm thick, for example. The n-type GaN contact layer 4 is 4μm thick, for example, and is doped with Si, for example, as its n-typeimpurity. The n-type AlGaN cladding layer 5 is 0.5 μm thick, forexample, and is doped with Si as its n-type impurity. The n-type GaNoptical guide layer 6 is 0.1 μm thick, for example, and is doped withSi, for example as its n-type impurity. The p-type AlGaN cap layer 8 is20 nm thick, for example, and Mg, for example, is doped as a p-typeimpurity. The p-type GaN optical guide layer 9 is 0.1 μm thick, forexample, and Mg, for example, is doped as a p-type impurity. The p-typeAlGaN cladding layer 10 is 0.5 μm thick, for example, and Mg, forexample, is doped as a p-type impurity. The p-type GaN contact layer 11is 0.2 μm thick, for example, and Mg, for example, is doped as a p-typeimpurity. Al composition ratio in the n-type AlGaN cladding layer 5 andthe p-type AlGaN cladding layer 10 is 0.07, for example, and Alcomposition ratio in the p-type AlGaN cap layer 8 is 0.16, for example.As to the active layer of the Ga_(1−x)In_(x)N/Ga_(1−y)In_(y)N multiquantum well structure, x=0.11, y=0.01, thicknesses of Ga_(1−x)In_(x)Nlayers and Ga_(1−y)In_(y)N layers are 3 nm and 6 nm, for example, andthe number of wells is four.

An upper-lying portion of the n-type GaN contact layer 4, n-type AlGaNcladding layer 5, n-type GaN optical guide layer 6, active layer 7 withthe Ga_(1−x)In_(x)N/Ga_(1−x)In_(y)N multi quantum well structure, p-typeGaN optical guide layer 9, p-type AlGaN cladding layer 10 and p-type GaNcontact layer 11 have a mesa configuration of a predetermined width. Aridge portion 12 of a predetermined width is formed in an upper-lyingportion of the p-type AlGaN cladding layer 10 and the p-type GaN contactlayer 11 in the mesa portion to extend in one direction. An insulatingfilm 13 such as SiO₂ film is provided on the surface of the mesa portionand the exposed surface of the n-type GaN contact layer 4 outside themesa portion. The insulating film 13 has formed an opening 13 a in alocation above the ridge portion 12 and an opening 13 b in a locationabove a part of the n-type GaN contact layer 4 adjacent to the mesaportion. A p-side electrode 14 is provided to straddle the ridge portion12, and it is brought into ohmic contact with the p-type GaN contactlayer 11 in the ridge portion 12 through the opening 13 a in theinsulating film 13. The p-side electrode 14 has a Ni/Pt/Au structuresequentially stacking a Ni film, Pt film and Au film, for example. Ann-side electrode 15 is formed on the n-type GaN contact layer 4 in ohmiccontact therewith through the opening 13 b in the insulating film 13.The n-side electrode 15 has a Ti/Al/Pt/Au structure sequentiallystacking a Ti film Al film, Pt film and Au film, for example.

As shown in FIG. 2, in the first embodiment, unlike a conventional GaNsemiconductor laser, a number of recesses 1 a are formed by a surfacedensity around 10⁹ cm⁻² on the c-plane sapphire substrate 1 along theboundary with the overlying nitride III-V compound semiconductor,namely, GaN buffer layer 2. Cross-sectional configurations of theserecesses 1 a may be various, such as triangles, trapezoids, etc., andtheir plan-view configurations may also various, like hexagons,triangles, circles, and their combinations, as shown in FIGS. 3A to 3F.Size of each recess 1 a is, for example, 25 nm or more in depth and 30nm or more in width. In these recesses 1 a, Al_(x)Ga_(1−x)N crystal 16uniform in crystalline orientation is plugged. Al composition ratio x ofthe Al_(x)Ga_(1−x)N crystal 16 is 0.2 or more. Distance of moire fringeobserved at the portion of the Al_(x)Ga_(1−x)N crystal 16 in an electronmicroscopic image obtained by exciting (0006) reflection of the sapphirecrystal and (0002) reflection of the GaN crystal is 1.37 through 1.67nm.

Next explained is a manufacturing method of the GaN semiconductor laseraccording to the first embodiment having the above-explainedconstruction.

For manufacturing the GaN semiconductor, first prepared is the c-planesapphire substrate 1 having a smoothed and polished surface, as shown inFIG. 4. The c-plane sapphire substrate 1 is introduced into a reactionvessel of a MOCVD apparatus, not shown.

After that, in the reaction vessel containing an atmosphere of hydrogengas, inactive gas such as argon gas, or nitrogen gas, more preferably, adeoxidizing atmosphere such as hydrogen gas, the product is annealed for1 to 60 minutes, setting the substrate temperature to 1000 through 1300°C., for example, the surface of the c-plane sapphire substrate 1 isprocessed by thermal cleaning, and recesses 1 a are made on the surfaceas shown in FIG. 5. In this process, the temperature and time areadjusted, depending on sizes and configurations of the recesses 1 a tobe made.

After that, the substrate temperature is decreased to 520° C., forexample, and the GaN buffer layer 2 is grown by MOCVD on the surface ofthe c-plane sapphire substrate 1 having formed the recesses 1 a. Then,the substrate temperature is increased to 1000° C., for example, andMOCVD is conducted to sequentially grow on the GaN buffer layer 2 theundoped GaN layer 3, n-type GaN contact layer 4, n-type AlGaN claddinglayer 5, n-type GaN optical guide layer 6, active layer 7 with theGa_(1−x)In_(x)N/Ga_(1−y)In_(y)N multi quantum well layer, p-type AlGaNcap layer 8, p-type GaN optical guide layer 9, p-type AlGaN claddinglayer 10 and p-type GaN contact layer 11. However, for growth of theactive layer 7 having the Ga_(1−x)In_(x)N/Ga_(1−y)In_(y)N multi quantumwell structure containing In, the substrate temperature is held in 700through 800° C. Source materials used for growth of these GaNsemiconductor layers are, for example, trimethyl gallium (TMG) as thesource material of a group III element Ga, trimethyl aluminum (TMA) asthe source material of a group III element Al, trimethyl indium (TMI) asthe source material of a group III element In, and ammonium (NH₃) as thesource material of a group V element N. Used as the carrier gas is amixed gas of hydrogen (H₂) and nitrogen (N₂), for example. Dopants usedhere are monosilane (SiH₄), for example, as the n-type dopant, andmethylcyclopentadienile magnesium ((MCp)₂Mg), for example, as the p-typedopant.

A sequence of substrate temperatures from the thermal cleaning to growthof nitride III-V compound semiconductor layers is shown in FIG. 6.

As a result of annealing while increasing the substrate temperatureafter growth of the GaN buffer 2, part of the GaN buffer layer pluggedinto the recesses 1 a on the c-plane sapphire substrate 1 iscrystallized by solid-phase epitaxial growth, and Al diffuses into thecrystal from the c-plane sapphire substrate 1. As a result,Al_(x)Ga_(1−x)N crystal 16 having a uniform crystalline orientation isformed inside the recesses 1 a. According to measurement of distancesbetween moire fringes through transmission electron microscopy, thismethod enables increasing the Al composition ratio x in theAl_(x)Ga_(1−x)N crystal 16 as large as 0.95 in maximum. Additionally, inthe process of this crystallization and diffusion of Al, the c-planesapphire substrate 1 and the Al_(x)Ga_(1−x)N crystal 16 firmly couple toeach other by commonly sharing Al. Furthermore, since theAl_(x)Ga_(1−x)N crystal 16 has smaller difference in lattice constantfrom that of the c-plane sapphire than GaN, the difference in latticeconstant between the c-plane sapphire substrate 1 and the GaN bufferlayer 2 is alleviated. Moreover, from the entire view of theAl_(x)Ga_(1−x)N crystal 16 and the GaN buffer layer 2 thereon, they forma structure where the Al composition ratio gradually decreases from thebottom to the top, and lattice mismatching withe c-plane sapphiresubstrate 1 is gradually alleviated. Thus, crystallization of the GaNbuffer layer 2 progresses from the Al_(x)Ga_(1−x)N crystal 16 as thecore, and a GaN buffer layer 2 with an excellent crystallographicproperty can be obtained finally. Accordingly, the undoped GaN layer 3,n-type GaN contact layer 4, n-type AlGaN cladding layer 5, n-type GaNoptical guide layer 6, active layer 7 with theGa_(1−x)In_(x)N/Ga_(1−y)In_(y)N multi quantum well layer, p-type AlGaNcap layer 8, p-type GaN optical guide layer 9, p-type AlGaN claddinglayer 10 and p-type GaN contact layer 11, which grow on thecrystallographically excellent GaN buffer layer 2, also result in havinggood crystallographic properties.

After that, a SiO₂ film which is 0.4 μm thick, for example, is formed onthe entire surface of the p-type GaN contact layer 11 by CVD, vacuumevaporation or sputtering, for example, and a resist pattern (not shown)of a predetermined configuration is formed on the SiO₂ film bylithography. Using the resist pattern as a mask, the SiO₂ film isselectively removed by wet etching using an etchant based on fluoricacid, for example, to form a mask (not shown) of the SiO₂ film on thep-type GaN contact layer 11.

Thereafter, using the mask, reactive ion etching (RIE) for example, isconducted to the depth reaching the n-type GaN contact layer 4, suchthat the n-type GaN contact layer 4 is removed by 0.5 μm, for example.Used as the etching gas for RIE is a chlorine-based gas, for example.

After that, the mask is removed, another SiO₂ film, which is 0.2 μm, forexample, is formed on the entire substrate surface by CVD, vacuumevaporation or sputtering, for example, and a resist pattern (not shown)of a predetermined configuration is made on the SiO₂ film bylithography. Using the resist pattern as a mask, the SiO₂ film isselectively removed by wet etching using an etchant based on fluoricacid, for example, to form a mask (not shown) of the SiO₂ film on thesubstrate surface including the mesa portion.

Subsequently, using the mask, etching by RIE, for example, is conductedto a predetermined depth in the thickness direction of the p-type GaNcontact layer 11 to form a groove as the ridge portion 12. Used as theetching gas for RIE is used a chlorine-based gas, for example.

Next made is a resist pattern (not shown) by lithography to cover thesurface of the region excluding the region for the n-side electrode.

Next using the resist pattern as a mask, the insulating film 13 ispartly removed by etching to make the opening 13 b.

Subsequently, after the Ti film, Al film, Pt film and Au film aresequentially stacked by vacuum evaporation, for example, on the ensuresurface of the substrate still covered by the resist pattern, the resistpattern is removed together with the overlying part of the Ti film, Alfilm, Pt film and Au film (lift-off). As a result, the n-side electrode15 with the Ti/Al/Pt/Au structure is formed on a location of the n-typeGaN contact layer 4 at the opening 13 b of the insulating film 13.

After that, by conducting annealing in a nitrogen gas atmosphere at 800°C. for 10 minutes, for example, to activate the p-type impurity dopedinto the p-type AlGaN cap layer 8, p-type GaN optical guide layer 9,p-type AlGaN cladding layer 10 and p-type GaN contact layer 11 and toalloy the n-side electrode 15.

Next made is a resist pattern (not shown) by lithography to cover thesurface of the region excluding the region of the ridge portion 12.

Then using the resist pattern as a mask, the insulating film 13 isselectively removed by etching to make the opening 13 a and therebyexpose the upper surface of the ridge portion 12.

Thereafter, another resist pattern (not shown) is made by lithography tocover the surface of the region excluding the region for the p-sideelectrode.

Then, after the Ni film, Pt film and Au film are sequentially stacked onthe entire surface of the substrate by vacuum evaporation, for example,the resist pattern is removed together with the overlying part of the Nifilm, Pt film and Au film. As a result, the p-side electrode 14 of theNi/Pt/Au structure is formed to straddle the ridge portion 12 as shownin FIG. 1. Thereafter, annealing is conducted in a nitrogen gasatmosphere at 600° C. for 20 minutes, for example, to alloy the p-sideelectrode 14.

Subsequently, after processing the c-plane sapphire substrate 1 havingformed the laser structure thereon into bars to make opposite cavityedges and coating the edges, the bars are divided into chips. As aresult, intended GaN semiconductor lasers with the ridge structure andthe SCH structure are obtained.

As explained above, according to the first embodiment, the GaN bufferlayer 2 is entirely crystallized by first making recesses 1 a on a majorsurface of the c-plane sapphire substrate 1, then growing the GaN bufferlayer 2 on the major surface at the substrate temperature of 520° C.,thereafter increasing the substrate temperature to 1000° C. so that partof the GaN buffer layer 2 plugged into the recesses 1 a be crystallizedby solid-phase growth while incorporating Al diffused thereto to formAl_(x)Ga_(1−x)N crystal 16, and then crystallizing the entire GaN bufferlayer 2 from the Al_(x)Ga_(1−x)N crystal 16 as the core. Therefore, theundoped GaN layer 3, n-type GaN contact layer 4, n-type AlGaN claddinglayer 5, n-type GaN optical guide layer 6, active layer 7 with theGa_(1−x)In_(x)N/Ga_(1−y)In_(y)N multi quantum well layer, p-type AlGaNcap layer 8, p-type GaN optical guide layer 9, p-type AlGaN claddinglayer 10 and p-type GaN contact layer 11, which grow on the GaN bufferlayer 2, also have excellent crystallographic properties. As a result,GaN semiconductor lasers with high performance, long lifetime and highreliability can be realized.

Next explained is the second embodiment of the invention.

In the second embodiment, similarly to the first embodiment, after therecesses 1 a are made on the surface of the c-plane sapphire substrate,the surface of the c-plane sapphire substrate 1 is exposed to a sourcematerial gas containing nitrogen, such as ammonium gas, under a hightemperature around 1000 C., for example, to nitrify it and thereby makea nitride layer containing Al and N. After that, the step of growing theGaN buffer layer 2 and subsequent steps are progressed similarly to thefirst embodiment to obtain an intended GaN semiconductor laser.

According to the second embodiment, the following advantages areobtained in addition to the same advantages as those of the firstembodiment. That is, since the GaN buffer laser 2 is grown after firstmaking the recesses 1 a on the surface of the c-plane sapphire substrate1 and then making the nitride layer on the surface, Al diffuses into theGaN buffer layer 2 while Ga diffuses into the nitride layer to thecontrary, due to diffusion and reaction of Al between the nitride layerand the GaN buffer layer 2 plugged into the recesses 1 a. As a result,diffusion of Al is greatly promoted, and this is advantageous for makingAl_(x)Ga_(1−x)N crystal 16 having a higher Al composition ratio x.

Next explained is the third embodiment of the invention.

As shown in FIG. 7, in a GaN semiconductor laser taken as the thirdembodiment of the invention, Al_(x)Ga_(1−x)N crystal 16 having a uniformcrystalline orientation is made on the entire interface between thec-plane sapphire substrate 1 and the GaN buffer layer 2 to bury therecesses 1 a. In the other respects, the laser shown here is the same asthe GaN semiconductor laser according to the first embodiment.

The third embodiment also ensures the same advantages as those of thefirst embodiment.

Next explained is the fourth embodiment of the invention.

In the fourth embodiment, after the recesses 1a are made on the surfaceof the c-plane sapphire substrate in the same manner as the firstembodiment, the substrate temperature is once decreased to 520° C., andgradually raised therefrom to 1000° C. to grow the undoped GaN layer 2directly on the c-plane sapphire substrate 1. Thereafter, the n-type GaNcontact layer 3 and other layers are grown thereon in the same manner asthe first embodiment. A sequence of substrate temperatures from thethermal cleaning to growth of the nitride III-V compound semiconductorlayers is shown in FIG. 8.

According to the fourth embodiment, since crystallization of the undopedGaN layers 2 starts from the recesses 1 a of the c-plane sapphiresubstrate 1, excellent crystallographic property is ensured throughoutthe entire undoped GaN layer 2, and this results in improving thecrystallographic property of the nitride III-V compound semiconductorlayer grown thereon.

Next explained is the fifth embodiment of the invention.

As shown in FIGS. 9 and 10, in a GaN semiconductor laser according tothe fifth embodiment, a plurality of straight recesses 1 a are made onthe surface of the c-lane sapphire substrate 1 to extend in parallelwith each other in one direction (for example, <11–20> direction), andAl_(x)Ga_(1−x)N crystal 16 is plugged into the recesses 1 a. In theother respects, the embodiment shown here is the same as the firstembodiment.

The GaN semiconductor laser according to the fifth embodiment can bemanufactured by the same manufacturing method of the GaN semiconductorlaser according to the first embodiment, except that the process ofmaking the recesses 1 a on the c-plane sapphire substrate is different.In the fifth embodiment, the recesses 1 a are made by first making aresist pattern (not shown) in form of predetermined stripes bylithography on the c-plane sapphire substrate 1 having a smoothed andpolished surface, and then etching the c-plane sapphire substrate 1 bydry etching to a predetermined depth, using the resist pattern as amask.

The fifth embodiment also ensures the same advantages as those of thefirst embodiment.

Next explained is the sixth embodiment of the invention.

As shown in FIGS. 11 and 12, in a GaN semiconductor laser according tothe sixth embodiment, recesses 1 a having a hexagonal plan-viewconfiguration are made in a two-dimensional array, and Al_(x)Ga_(1−x)Ncrystal 16 is buried into the recesses 1 a. In the other respects, theembodiment shown here is the same as the first embodiment.

The GaN semiconductor laser according to the sixth embodiment can bemade by the same manufacturing method of the GaN semiconductor laseraccording to the first embodiment, except that the process of making therecesses 1 a on the c-plane sapphire substrate is different. That is, inthe sixth embodiment, the recesses 1 a are made by first making a resistpattern (not shown) of an arrangement of predetermined hexagons bylithography on the sapphire substrate with a smoothed and polishedsurface, and next etching the c-plane sapphire substrate 1 to apredetermined depth by dry etching, using the resist pattern as a mask.

The sixth embodiment also ensures the same advantages as those of thefirst embodiment.

Having described specific preferred embodiments of the present inventionwith reference to the accompanying drawings, it is to be understood thatthe invention is not limited to those precise embodiments, and thatvarious changes and modifications may be effected therein by one skilledin the art without departing from the scope or the spirit of theinvention as defined in the appended claims.

For example, numerical values, structures, source materials andprocesses introduced in the explanation of the first to sixthembodiments are not but examples, and any other appropriate numericalvalues, structures, source materials and processes may be used.

The first to fourth embodiment have been explained as making therecesses 1 a by thermal cleaning of the surface of the c-plane sapphiresubstrate in a reaction vessel of a MOCVD apparatus. However, it alsopossible to first use a different apparatus for making the recesses 1 aby thermal cleaning of the surface of the c-plane sapphire substrate,then moves the c-plane sapphire substrate 1 to the reaction vessel of aMOCVD apparatus to once again conduct thermal cleaning and thereaftergrow the layers.

In the first to third, fifth and sixth embodiments, the GaN buffer layer2 is grown as the buffer layer. However, generally usable as the bufferlayer is a Ga_(1−x−y)In_(y)N (0≦x≦1, 0≦y≦1, 0≦x+y≦1) layer.

Although the first to sixth embodiments have been explained as applyingthe invention to GaN semiconductor lasers having a SCH structure, theinvention is also applicable to GaN semiconductor lasers having a DHstructure (double heterostructure). It is possible to use a singlequantum well structure to form the active layer 7. From the viewpoint oflaser structure, the invention can employ various types of laserstructures such as ridge-guided structure, internal current blockingstructure, structural substrate type, longitudinal mode controlstructure (lasers of a distributed feedback (DFB) type or distributedBragg reflection type (DBR) which realize gain-guided structures orindex-guided structures. Additionally, the invention is also applicableto GaN light emitting diodes, and GaN FETs or other electron mobilitydevices.

As described above, according to the invention, since a plurality ofrecesses are made on a major surface of a sapphire substrate, growth ofa nitride III-V compound semiconductor layer on the sapphire substratecan be controlled by a plurality of crystalline directions andcrystalline surfaces. Therefore, accurate coincidence in crystallineorientation is ensured between the sapphire substrate and the nitrideIII-V compound semiconductor grown thereon, and the nitride III-Vcompound semiconductor is therefore ensured to exhibit excellentcrystallographic property.

1. A manufacturing method of a semiconductor device using a nitrideIII-V compound semiconductor layer grown on a sapphire substratecomprising: first forming recesses on a major surface of said sapphiresubstrate using thermal cleaning, and thereafter growing said nitrideIII-V compound semiconductor layer on said major surface of saidsapphire substrate, wherein said nitride III-V compound semiconductorlayer is grown after first growing a buffer layer made of a nitrideIII-V compound semiconductor on said major surface of the sapphiresubstrate at a first substrate temperature, while raising the substratetemperature from said first temperature to a second temperature higherthan said first temperature, and wherein each said recess has a depthnot less than 10 nm and a width not less than 30 nm.
 2. Themanufacturing method of a semiconductor device according to claim 1wherein said major surface of said sapphire substrate is nitrided priorto growth of said buffer layer.
 3. A manufacturing method of asemiconductor device using a nitride III-V compound semiconductor layergrown on a sapphire substrate comprising: first forming recesses on amajor surface of said sapphire substrate, and thereafter growing saidnitride III-V compound semiconductor layer on said major surface of saidsapphire substrate; wherein a buffer layer made of a nitride III-Vcompound semiconductor is grown on said sapphire substrate while raisingthe substrate temperature from a first temperature to a secondtemperature higher than said first temperature, and wherein each saidrecess has a depth not less than 10 nm and a width not less than 30 nm.4. The manufacturing method of a semiconductor device according to claim3 wherein said major surface of said sapphire substrate is nitridedprior to growth of said buffer layer.
 5. A manufacturing method of asemiconductor device using a nitride III-V compound semiconductor layergrown on a sapphire substrate comprising: first forming recesses on amajor surface of said sapphire substrate, and thereafter growing saidnitride III-V compound semiconductor layer on said major surface of saidsapphire substrate; wherein said nitride III-V compound semiconductorlayer is grown directly on said sapphire substrate while raising thesubstrate temperature from a first temperature to a second temperaturehigher than said first temperature, and wherein each said recess has adepth not less than 10 nm and a width not less than 30 nm.
 6. Themanufacturing method of a semiconductor device according to claim 5wherein said major surface of said sapphire substrate is nitrided priorto growth of said nitride III-V compound semiconductor layer.